CN108948456A - Conductive rubber composition, transfer roll and image forming apparatus - Google Patents

Conductive rubber composition, transfer roll and image forming apparatus Download PDF

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Publication number
CN108948456A
CN108948456A CN201810268757.7A CN201810268757A CN108948456A CN 108948456 A CN108948456 A CN 108948456A CN 201810268757 A CN201810268757 A CN 201810268757A CN 108948456 A CN108948456 A CN 108948456A
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China
Prior art keywords
rubber
mass parts
transfer roll
rubber composition
resistance value
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Pending
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CN201810268757.7A
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Chinese (zh)
Inventor
小坂圭亮
谷尾勇祐
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Sumitomo Rubber Industries Ltd
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Sumitomo Rubber Industries Ltd
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Publication of CN108948456A publication Critical patent/CN108948456A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/14—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base
    • G03G15/16—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0033—Use of organic additives containing sulfur
    • C—CHEMISTRY; METALLURGY
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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    • C08K5/00—Use of organic ingredients
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C08L71/03—Polyepihalohydrins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/14—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base
    • G03G15/16—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer
    • G03G15/1665—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer by introducing the second base in the nip formed by the recording member and at least one transfer member, e.g. in combination with bias or heat
    • G03G15/167—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer by introducing the second base in the nip formed by the recording member and at least one transfer member, e.g. in combination with bias or heat at least one of the recording member or the transfer member being rotatable during the transfer
    • G03G15/1685—Structure, details of the transfer member, e.g. chemical composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • C—CHEMISTRY; METALLURGY
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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    • C08J2205/00—Foams characterised by their properties
    • C—CHEMISTRY; METALLURGY
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    • C08J2307/00—Characterised by the use of natural rubber
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
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    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides
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    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/02—Copolymers with acrylonitrile
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    • C08J2409/06—Copolymers with styrene
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    • C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
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    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/14—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base
    • G03G15/16—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer
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Abstract

The present invention, which provides, to be become the conductive rubber composition of the raw material of roller main body, has the transfer roll of the roller main body formed using the conductive rubber composition and be assembled with the image forming apparatus of above-mentioned transfer roll, the conductive composition is capable of forming following transfer rolls, and roller resistance value when changing small, continuous energization of transfer roll roller resistance value due to caused by the difference of use environment rises image that is small, being continuously formed good quanlity.The conductive rubber composition crosslinking ingredient of mixture and foaming ingredient in the rubber comprising 20 mass parts~30 mass parts epichlorohydrin rubber in 100 mass parts of SBR and/or NBR and rubber total amount; and relative to every 100 mass parts of rubber total amount, mixture has the sylvite in the molecule with fluorine-based and sulfonyl anion of 0.01 mass parts or more 1 below the mass.Transfer roll (1) has the roller main body (2) being made of above-mentioned conductive rubber composition.Image forming apparatus is assembled with above-mentioned transfer roll.

Description

Conductive rubber composition, transfer roll and image forming apparatus
Technical field
The present invention relates to conductive rubber composition, has the transfer of the roller main body being made of the conductive rubber composition Roller and the image forming apparatus for being assembled with the transfer roll.
Background technique
Electronics is utilized in laser printer, electrostatic duplicator, plain paper facsimile device or their equipment complex etc. In the image forming apparatus of photographic process, in order to which the toner picture that will be formed on photoreceptor is transferred to the table of the paper such as paper or plastic foil Face etc., uses transfer roll.
As transfer roll, it is generally configured with the roller main body being made of conductive rubber composition, the conductive rubber composition It is that mixture is used to make the crosslinking component of the rubber cross and generates the above-mentioned for making of gas by heat resolve in rubber The foaming agent of rubber pange simultaneously assigns made of electric conductivity.That is, above-mentioned conductive rubber composition is shaped to tubular, while into Row heating makes it be crosslinked and foam, and roller main body is consequently formed, and manufactures transfer roll.As the rubber for the raw material for becoming roller main body, most Commonly nitrile rubber (NBR).
Following researchs have been carried out in patent document 1: replacing NBR using SBR styrene butadiene rubbers (SBR), and Blowing promotor is shared together with foaming agent, adjusts the mixed ratio of the foaming agent, blowing promotor, which plays reduction The decomposition temperature of the foaming agent come promote decompose effect.
According to this constitution, the unit price due to SBR ratio NBR is cheap, it is thus possible to cut down the manufacturing cost of transfer roll.In addition, It by making its foaming, can reduce using material and further cost effective, and transfer roll lightweight can also be made and cut down The costs such as freight.
Moreover, by adjusting separately the mixed ratio of foaming agent and blowing promotor for defined range, additionally it is possible to assign Roller main body is suitable as the flexibility of the appropriateness of transfer roll, while the bubble diameter of foam bubble can also be made to become smaller, and improves roller master The flatness of the outer peripheral surface of body.
That is, the decomposition temperature of foaming agent reduces, thus pole of the foaming agent after beginning to warm up in mixed blowing promotor In short time, it can almost decompose and foam simultaneously in the substantially entirety of cylindrical body.Also, pass through the origin of foaming prolonged expansion Mutually inhibit to expand due to mutual exapnsion power between adjacent foam bubble in the foam bubble of foaming agent, it is as a result each Bubble diameter becomes smaller.
Therefore, according to the transfer roll for having above-mentioned roller main body, the reduction of cost can be reached as described above, while can also The flatness of the outer peripheral surface of roller main body is improved, the image quality for forming image is improved.
As the rubber for forming roller main body, shared together with SBR in patent document 1 for assigning the roller main body ion The ethylene propylene diene rubber (EPDM) of the epichlorohydrin rubber of electric conductivity and the ozone resistance for improving roller main body.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2015-34878 bulletin
Summary of the invention
Problems to be solved by the invention
In recent years, along with the globalization in image forming apparatus market, use environment is moving towards diversification, for figure As forming device, it is desirable that be capable of forming the stable aesthetic image of image quality under any use environment.
But according to the inventor's study, for imparting ion by epichlorohydrin rubber plasma conducting rubber There is the variation of roller resistance value caused by the difference due to use environment, the i.e. difference of temperature or humidity in the transfer roll of electric conductivity Big project.Also, as setting is assembled with the difference in the place of the image forming apparatus of transfer roll or even if for identical field But weather, variation of weather etc., the roller resistance value of transfer roll may also dramatically change, can to image color etc. formed image Image quality affect.
Such as carried out following researchs: mixture has ion with fluorine-based and sulfonyl salt of anion etc. in the molecule Electric conductivity and molecular weight are less than the salt (hereinafter sometimes called " ion salt ") of the cross-linking agent of rubber to replace ionic conductivity Rubber prepares conductive rubber composition.According to the inventor's study, if forming roller master using the conductive rubber composition Body can reduce then compared with the transfer roll being made of the conductive rubber composition comprising ionic conductivity rubber due to making The variation of the roller resistance value of transfer roll caused by difference with environment.
But if continuously to turn for having the roller main body being made of the conductive rubber composition comprising above-mentioned ion salt Print roller carries out continuing energization, then the roller resistance value of the transfer roll is substantially increased compared with initial value, is existed to shapes such as image colors The project affected at the image quality of image.It is main reason is that ion salt is influenced in continuous be powered by external electrical field And it is moved in roller main body.That is, as noted previously, as the molecular weight of ion salt is smaller than the cross-linking agent of rubber and its structure The reason of, cause the ion salt to be easy the influence by external electrical field and move in roller main body.
Result, it is believed that for example equally distributed ion salt is moved due to being continuously powered in roller main body under state in the early stage Near to the outer peripheral surface of roller main body or bloom (precipitation) on outer peripheral surface of mobile ion salt has occurred, makes in roller main body Ion salt there are ratio reduce or distribution generate deviation, be as a result substantially increased the roller resistance value of transfer roll.Moreover, The reason of ion salt on bloom to surface can also pollute photoreceptor etc., become the image quality reduction to form image.
The purpose of the present invention is to provide a kind of conductive rubber composition of raw material as roller main body, the electric conductivity rubbers Glue composition is capable of forming following transfer rolls, the variation of transfer roll roller resistance value due to caused by the difference of use environment is small, The rising of roller resistance value when continuous energization is small, and roller resistance value is stablized, it is thus possible to be formed continuously the image of good quanlity.Separately Outside, the purpose of the present invention is to provide the transfer roll for having the roller main body formed using above-mentioned conductive rubber composition and It is assembled with the image forming apparatus of the transfer roll.
Means for solving the problems
The present invention is conductive rubber composition, and crosslinking component it includes rubber, for making above-mentioned rubber cross is used for Make the foaming ingredient of above-mentioned rubber pange and in the molecule with the sylvite of fluorine-based and sulfonyl anion, above-mentioned rubber bag Containing selected from by least one of SBR and NBR group formed and epichlorohydrin rubber, above-mentioned epichlorohydrin rubber is mixed With ratio be 20 mass parts in above-mentioned 100 mass parts of rubber total amount or more 30 below the mass, and relative to above-mentioned rubber Every 100 mass parts of total amount, the mixed ratio of above-mentioned sylvite be 0.01 mass parts or more 1 below the mass.
In addition, the present invention is to have the cylinder being made of the crosslinking of the conductive rubber composition of aforementioned present invention, foamed The transfer roll of the roller main body of shape, and it is assembled with the image forming apparatus of the transfer roll.
Invention effect
In accordance with the invention it is possible to a kind of conductive rubber composition of raw material as roller main body is provided, the electric conductivity rubber Glue composition is capable of forming following transfer rolls, the variation of transfer roll roller resistance value due to caused by the difference of use environment is small, The rising of roller resistance value when continuous energization is small, and roller resistance value is stablized, it is thus possible to be formed continuously the image of good quanlity.Separately Outside, in accordance with the invention it is possible to provide the transfer roll and group for having the roller main body formed using above-mentioned conductive rubber composition Image forming apparatus equipped with the transfer roll.
Detailed description of the invention
Fig. 1 is the perspective view for showing the appearance of an example of embodiment of transfer roll of the invention.
Fig. 2 is the figure being illustrated to the method for the roller resistance value of measurement transfer roll.
Specific embodiment
" conductive rubber composition "
The present invention is conductive rubber composition, and crosslinking component it includes rubber, for making above-mentioned rubber cross is used for Make that especially there is fluorine-based and sulfonyl anion in the molecule in the foaming ingredient and ion salt of above-mentioned rubber pange Sylvite (hereinafter sometimes called " sylvite "), above-mentioned rubber include selected from by least one of SBR and NBR group formed, And epichlorohydrin rubber, the mixed ratio of above-mentioned epichlorohydrin rubber are 20 matter in above-mentioned 100 mass parts of rubber total amount Measure part or more 30 below the mass, and relative to every 100 mass parts of above-mentioned rubber total amount, the mixed ratio of above-mentioned sylvite is It is more than 0.01 mass parts that 1 below the mass.
When forming roller main body using the conductive rubber composition of the invention, even if utilizing the shadow by external electrical field The cross-linking agent of mobile epichlorohydrin rubber will not occur in roller main body for sound, it can be ensured that in entire roller main body substantially The rising of uniform ionic conductivity, the roller resistance value for inhibiting continuous when being powered, and by sharing above-mentioned a small amount of sylvite, energy Enough variations for inhibiting the roller resistance value due to caused by the difference of use environment.
To which conductive rubber composition according to the present invention is capable of forming the roller main body of following transfer rolls, the transfer roll The variation of the roller resistance value due to caused by the difference of use environment is small, continuous energization when roller resistance value rising it is small, roller resistance Value is stablized, it is thus possible to be continuously formed the image of good quanlity.
In addition, conductive rubber composition according to the present invention, by sharing sylvite and epichlorohydrin rubber, institute as above State the roller master that the mixed ratio of two kinds of ingredients can be made to be made of respectively than usually few and imparting the conductive rubber composition The good ionic conductivity of body, the roller resistance value that can will be provided with the transfer roll of the roller main body are set to be suitable for the transfer roll Range.It is thus possible to enough cut down the manufacturing cost of transfer roll.Especially SBR is being selected to close as with epichlorohydrin rubber In the case where rubber, since the mixed ratio of the high SBR of cost advantage can be increased, it is thus possible to further reduce at This.
< epichlorohydrin rubber >
As epichlorohydrin rubber, it is able to use comprising epoxychloropropane as repetitive unit and with ionic conductivity Various polymer.
As epichlorohydrin rubber, it can be cited for example that epichlorohydrin homopolymers, epoxychloropropane-ethylene oxide two Membered copolymer (ECO), epoxychloropropane-propylene oxide bipolymer, epoxychloropropane-allyl glycidyl ether binary Copolymer, epoxychloropropane-ethylene oxide-allyl glycidyl ether terpolymer (GECO), epoxychloropropane-epoxy Propane-allyl glycidyl ether terpolymer, epoxychloropropane-epoxy ethane-epoxy propane-allyl glycidol It is one kind or two or more in base ether quadripolymer etc..
Wherein, it is shared in system with above-mentioned sylvite, is suitable as turning from the roller resistance value of the transfer roll to be reduced to From the aspect of the effect for printing the range of roller, the copolymer, particularly preferred ECO and/or GECO of ethylene oxide are preferably comprised.
Ethylene oxide content in above two copolymer is both preferably 30 moles of % or more, particularly preferably 50 moles of % More than, preferably 80 moles of % or less.
Ethylene oxide plays the role of reducing the roller resistance value of transfer roll.But it is less than the range in ethylene oxide content When, the effect cannot be sufficiently obtained, thus it is possible to the roller resistance value for being unable to fully reduce transfer roll.On the other hand, epoxy second In the case that alkane content is more than above range, ethylene oxide occurs crystallization, interferes the sub-chain motion of strand, thus deposits instead In the trend that the roller resistance value of transfer roll rises.In addition, the roller main body after crosslinking and foaming becomes really up to the mark, existing cannot be suitable for The possibility of the flexibility of appropriateness as transfer roll, or viscosity of the conductive rubber composition in heating melting before crosslinking It increases, there are the possibility that the processability of the conductive rubber composition and foaminess reduce.
Epichlorohydrin content in ECO is the surplus of ethylene oxide content.That is, epichlorohydrin content is preferably 20 to rub You are % or more, preferably 70 moles of % or less, particularly preferably 50 moles of % or less.
In addition, the allyl glycidyl ether content in GECO is preferably 0.5 mole of % or more, particularly preferably 2 rubs You are % or more, preferably 10 moles of % or less, particularly preferably 5 moles of % or less.
The function for ensuring free volume is played, thus itself as side chain for allyl glycidyl ether The crystallization for inhibiting ethylene oxide plays the role of the roller resistance value for reducing transfer roll.But allyl glycidyl ether contains When amount is less than the range, the effect cannot be sufficiently obtained, thus is possible to the roller resistance value for being unable to fully reduce transfer roll.It is another Aspect, since allyl glycidyl ether is functioned in the crosslinking of GECO as crosslinking points, thus in allyl glycidyl In the case that glyceryl ether content is more than above range, the crosslink density of GECO becomes excessively high, thus interferes the segment of strand There is the trend that the roller resistance value of transfer roll rises instead in movement.
Epichlorohydrin content in GECO is the surplus of ethylene oxide content and allyl glycidyl ether content. That is, epichlorohydrin content is preferably 10 moles of % or more, particularly preferably 19.5 moles of % or more, preferably 69.5 moles of % Below, 60 moles of % or less are particularly preferably.
It should be noted that not only having the copolymerization made made of 3 kinds of monomer copolymerization in the narrow sense being described above as GECO Object, but also it has been known that there is change epoxychloropropane-ethylene oxide bipolymer (ECO) with allyl glycidyl ether Modifier made of property.In the present invention, the GECO of any one of them can be used.These epoxychloropropane rubbers can be used It is one kind or two or more in glue.
〈SBR〉
As SBR, styrene and butadiene are copolymerized using the various polymerizations such as emulsion polymerization, solution polymerization process and closed At and can be used with the various SBR of bridging property.
As SBR, the SBR according to the high-phenylethylene type of styrene-content classification, middle styrene type and low-styrene type is equal It can be used.
In addition, having addition extending oil as SBR and having adjusted the oil-filled type SBR of flexibility and do not add the non-of extending oil Oil-filled type SBR, in the present invention, the pollution of photoreceptor is not, it is preferable to use include the increment that can become exudation substance in order to prevent The non-oil-filled type SBR of oil.It can be used one kind or two or more in these SBR.
〈NBR〉
As NBR, acrylonitrile and butadiene is copolymerized using the various polymerizations such as emulsion polymerization and synthesize and have The various NBR of bridging property can be used.
As NBR, acrylonitrile content is 24% low nitrile NBR below, acrylonitrile content is 25%~30% middle nitrile NBR, acrylonitrile content are the high nitrile NBR that high nitrile NBR, acrylonitrile content are 36%~42% in 31%~35%, acrylonitrile The high nitrile NBR that content is 43% or more can be used.
In addition, having addition extending oil as NBR and having adjusted the oil-filled type NBR of flexibility and do not add the non-of extending oil Oil-filled type NBR, in the present invention, for the purposes of preventing the pollution of photoreceptor, it is preferable to use do not include the increasing that can become exudation substance Measure the non-oil-filled type NBR of oil.It can be used one kind or two or more in these NBR.
Other rubber of < >
As rubber, it can according to need and further share selected from by EPDM, neoprene (CR) and acrylic rubber (ACM) at least one of the group formed.Wherein, when sharing EPDM, it can be improved the ozone resistance of roller main body as described above. In addition, capableing of the roller resistance value of micro-adjustment transfer roll when sharing CR and/or ACM as polar rubber.In addition, not sending out Bubble is uneven, is capable of forming porous structure as uniform as possible.It should be noted that from the aspect of the effect, as pole The preferred CR of property rubber.
(EPDM)
As EPDM, imported in main chain and a small amount of the 3rd ingredient (diene ingredient) is added in ethylene and propylene Various EPDM made of double bond can be used.
As EPDM, various products can provide according to the difference of the type of the 3rd ingredient and amount.As representative the 3 one-tenth Point, it can be cited for example that ethylidene norbornene (ENB), Isosorbide-5-Nitrae-hexadiene (Isosorbide-5-Nitrae-HD), dicyclopentadiene (DCP) etc..As Polymerization catalyst, usually using Ziegler catalyst.
In addition, having addition extending oil as EPDM and having adjusted the oil-filled type EPDM of flexibility and do not add extending oil Non- oil-filled type EPDM, in the present invention, for the purposes of preventing the pollution of photoreceptor, it is preferable to use do not include that exudation substance can be become Extending oil non-oil-filled type EPDM.It can be used one kind or two or more in these EPDM.
(CR)
It can be used as CR, the various CR with bridging property for making chloroprene emulsion polymerization and synthesizing.CR according to The type of the molecular weight regulator used when chloroprene emulsion polymerization is set to be classified into sulphur modification type and non-sulphur modification type.
Wherein, the CR of sulphur modification type be as by chlorobutadiene and as molecular weight regulator sulphur copolymerization obtained from gather It closes object thiuram disulfides etc. and carries out plasticized, be adjusted to defined viscosity and synthesize.
In addition, the CR of non-sulphur modification type is classified into such as mercaptan modified type, xanthic acid modified version.
The CR of mercaptan modified type uses the alkyl mercapto such as n-dodecyl mercaptan, tert-dodecylmercaotan, octyl mercaptan Alcohols synthesizes in the same manner as the CR of sulphur modification type in addition to this as molecular weight regulator.In addition, the CR of xanthic acid modified version makes It uses alkyl xanthogenic acid compound as molecular weight regulator, is still synthesized in the same manner as the CR of sulphur modification type in addition to this.
Based on crystallization rate, CR is classified into the slow type of the crystallization rate, medium type and fast type.? In the present invention, any type of CR can be used, wherein it is preferred that the CR of non-sulphur modification type and crystallization rate slow type.
In addition, the copolymer of chlorobutadiene Yu other copolymer compositions can be used as CR.As this, other are copolymerized into Point, it can be cited for example that 2,3- bis- chloro-1,3-butadienes, 1- chloro-1,3-butadiene, styrene, acrylonitrile, methacrylonitrile, It is one kind or two or more in isoprene, butadiene, acrylic acid, acrylate, methacrylic acid and methacrylate etc..
In turn, as CR, there is addition extending oil and have adjusted the oil-filled type CR of flexibility and do not add the non-of extending oil and fill Oil type CR, in the present invention, for the purposes of preventing the pollution of photoreceptor, it is preferable to use do not include the increment that can become exudation substance The non-oil-filled type CR of oil.It can be used one kind or two or more in these CR.
The mixed ratio > of < rubber
As described above, the mixed ratio of epichlorohydrin rubber needs for 20 mass parts in 100 mass parts of rubber total amount Above 30 below the mass.
It, cannot be by the mixed epichlorohydrin rubber institute band when mixed ratio of epichlorohydrin rubber is less than the range The above-mentioned effect for ensuring the substantially uniform ionic conductivity in entire roller main body come.In addition, in order to which the roller of transfer roll is electric Resistance value is adjusted to be suitable for the range of the transfer roll, needs a large amount of mixed sylvite, relative to every 100 mass parts of rubber total amount, The mixed sylvite more than 1 mass parts, so that the sylvite amount moved in roller main body increases in continuous be powered.Therefore, these feelings Condition concurs, and in continuous be powered, roller resistance value is substantially increased.In addition, sharing epichlorohydrin rubber and sylvite institute band The effect of the manufacturing cost of the reduction transfer roll come is also insufficient.
On the other hand, in the case where the mixed ratio of epichlorohydrin rubber is more than above range, even if sharing sylvite, The variation of roller resistance value due to caused by the difference of use environment also increases.In addition, by sharing epichlorohydrin rubber and sylvite The effect of the brought manufacturing cost for cutting down transfer roll is also insufficient.
In contrast, it by the way that the mixed ratio of epichlorohydrin rubber is set as above-mentioned range, is capable of forming following The roller main body of transfer roll, the variation of transfer roll roller resistance value due to caused by the difference of use environment is small, continuous energization when The rising of roller resistance value is small, and roller resistance value is stablized, it is thus possible to be continuously formed the image of good quanlity.In addition it is possible to cut Subtract the manufacturing cost of transfer roll.
In the case where other rubber such as not mixed EPDM, the mixed ratio of SBR and/or NBR are epichlorohydrin rubber Surplus.That is, the mixed ratio of SBR and/or NBR be 100 mass parts of rubber total amount in 70 mass parts more than 80 mass parts with Under.About the mixed ratio, in only SBR or in the case that only NBR is individually shared with epichlorohydrin rubber, for the SBR or NBR Mixed ratio；In the case where sharing SBR and NBR, for its total mixed ratio.
In addition, the said effect as brought by mixed other rubber in order to obtain, in the case where other mixed rubber Mixed ratio is preferably 5 mass parts in 100 mass parts of rubber total amount or more, and preferably 30 below the mass.SBR and/or NBR Mixed ratio be epichlorohydrin rubber and other rubber surplus.That is, the mixed ratio of SBR and/or NBR is preferably More than 40 mass parts in 100 mass parts of rubber total amount, preferably 75 below the mass.
< sylvite >
As composition sylvite in the molecule with fluorine-based and sulfonyl anion, it can be cited for example that fluoro-alkyl sulphur 1 kind in acid ion, bis- (fluoro-alkyl sulfonyl) imines ions, three (fluoro-alkyl sulfonyl) methide ions etc. or Two or more.
Wherein, as fluoroalkyl sulfonic acid radical ion, it can be cited for example that CF3SO3 -、C4F9SO3 -At least one of Deng.
In addition, as bis- (fluoro-alkyl sulfonyl) imines ions, it can be cited for example that (CF3SO2)2N-、(C2F5SO2)2N-、(C4F9SO2)(CF3SO2)N-、(FSO2C6F4)(CF3SO2)N-、(C8F17SO2)(CF3SO2)N-、(CF3CH2OSO2)2N-、 (CF3CF2CH2OSO2)2N-、(HCF2CF2CH2OSO2)2N-、[(CF3)2CHOSO2]2N-It is one kind or two or more in.
In turn, as three (fluoro-alkyl sulfonyl) methide ions, it can be cited for example that (CF3SO2)3C-、 (CF3CH2OSO2)3C-At least one of Deng.
It should be noted that lithium salts, sodium salt of above-mentioned anion etc. is also used extensively as ion salt.But due to lithium Salt and sodium salt have high-hygroscopicity and hygroscopy, thus for example deliquesce under high temperature, high humidity environment, are easy in transfer roll Outer peripheral surface bloom.If also, the ion salt bloom deliquesced, ion salt in roller main body reduced there are ratio or Distribution generates deviation, so that the roller resistance value of transfer roll be made to be substantially increased, or pollutes photoreceptor in the ion salt of surface bloom Deng and make to be formed the reduction of the image quality of image.
In contrast, since hygroscopicity, the hygroscopy of the sylvite of above-mentioned anion are low, thus even if in high temperature, high humidity ring It will not be deliquesced under border, thus will not be in the outer peripheral surface bloom of transfer roll, and the roller resistance value of transfer roll will not be made big Width rises, will not pollute photoreceptor and makes to form the reduction of the image quality of image.
In addition, sylvite will not be made to generate mass change in metering or be deliquesced due to moisture absorption, it is thus possible to compare appearance Easily metering precise volume, also having can make the hygroscopic capacity of every batch of Semiconductive rubber composition not allow the processing for being also easy to produce deviation etc. The excellent advantage of property.
As sylvite, from the effect or improves the ionic conductivity of conductive rubber composition, reduces the roller of transfer roll From the aspect of the effect of resistance value, preferably (CF3SO2)2NK [bis- (trifluoromethane sulfonyl group) imines potassium].
As discussed previously with respect to every 100 mass parts of rubber total amount, the mixed ratio of sylvite needs to be more than 0.01 mass parts 1 below the mass.
When the mixed ratio of sylvite is less than the range, the sylvite and epichlorohydrin rubber cannot be shared brought Inhibit the effect of the variation of roller resistance value due to caused by the difference of use environment.Therefore, in order to by the roller resistance value of transfer roll It is adjusted to be suitable for the range of the transfer roll, needs a large amount of mixed epichlorohydrin rubber, be more than 100 mass parts of rubber total amount In 30 mass parts, correspondingly, above-mentioned variation increases.In addition, epichlorohydrin rubber and sylvite are shared brought reduction The effect of the manufacturing cost of transfer roll is also insufficient.
On the other hand, in the case that the mixed ratio of sylvite is more than above range, in order to by the roller resistance value tune of transfer roll It is made into the range for being suitable for the transfer roll, it is necessary to the mixed ratio of epichlorohydrin rubber be made to be less than 100 mass of rubber total amount 20 mass parts in part, to cannot get above-mentioned brought by the mixed epichlorohydrin rubber ensure in entire roller main body greatly Cause the effect of uniform ionic conductivity.Therefore, the sylvite amount moved in roller main body increases, correspondingly, in continuous be powered, Roller resistance value is substantially increased.In addition, epichlorohydrin rubber and sylvite are shared the brought manufacturing cost for cutting down transfer roll Effect it is also insufficient.
In contrast, by the way that the mixed ratio of sylvite to be set in above-mentioned range, it is capable of forming the roller of following transfer rolls Main body, the variation of transfer roll roller resistance value due to caused by the difference of use environment is small, continuous energization when roller resistance value Rise small, roller resistance value stabilization, it is thus possible to be continuously formed the image of good quanlity.In addition it is possible to cut down transfer roll Manufacturing cost.
< crosslinking component >
As for making the crosslinking component of rubber cross, crosslinking agent, crosslinking accelerator etc. can be enumerated.
(crosslinking agent)
As crosslinking agent, it can be cited for example that sulphur system crosslinking agent, thiocarbamide system crosslinking agent, pyrrolotriazine derivatives system crosslinking agent, mistake It is one kind or two or more in oxide cross linking agent, various monomers etc..Particularly preferred sulphur system crosslinking agent.
As sulphur system crosslinking agent, it can be cited for example that powder sulphur, oil processing powder sulphur, sedimentation sulphur, colloid sulphur, dispersed sulphur Equal sulphur；Or tetramethyl thiuram disulfide, N, sulfur-containing organic compounds such as N- morpholine double dithio etc., particularly preferred sulphur.
In view of being crosslinked rubber well, productivity manufacture well have be suitable as transfer roll appropriateness When the transfer roll of flexibility and the small roller main body of compression set, relative to every 100 mass parts of rubber total amount, the mixture of sulphur Ratio is preferably 0.5 mass parts or more, and preferably 2 below the mass.
It should be noted that such as in the case where using oil processing powder sulphur, dispersed sulphur as sulphur, above-mentioned mixture Ratio refers to the ratio of sulphur of effective component meter contained in each substance itself.
In addition, its mixed ratio is preferably adjusted in the case where using sulfur-containing organic compound as crosslinking agent, so that Sulphur contained in molecule is above-mentioned range relative to the ratio of every 100 mass parts of rubber total amount.
(crosslinking accelerator)
As the crosslinking accelerator combined with sulphur system crosslinking agent, it can be cited for example that calcium hydroxide, magnesia (MgO), lead and yellow-collation (PbO) etc. one kind or two or more in inorganic accelerators or organic accelerator etc..In addition, can be enumerated as organic accelerator Such as in thiazole system promotor, thiuram system promotor, sulfenamide system promotor, dithiocar-bamate system promotor etc. It is one kind or two or more.Wherein preferably thiazole system promotor is shared with thiuram system promotor.
As thiazole system promotor, it can be cited for example that 2-mercaptobenzothiazole, two -2-[4-morpholinodithio based bisulfides, The zinc salt of 2-mercaptobenzothiazole, the cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (N, N- diethyl thiocarbamoyl sulphur Generation) it is one kind or two or more in benzothiazole, 2- (4 '-morpholinodithio) benzothiazole etc..Particularly preferred two -2- benzo thiophene Oxazolyl disulphide.
In addition, as thiuram system promotor, it can be cited for example that tetra methylthiuram list sulfide, tetra methylthiuram Disulphide, Thiuram disulphide, tetrabutyl thiuram disulfides, four (2- ethylhexyl) thiuram curing It is one kind or two or more in object, double pentamethylene thiuram tetrasulfides etc..Particularly preferred tetra methylthiuram list sulfide.
In sharing in system for above-mentioned 2 kinds of crosslinking accelerators, it is contemplated that when sufficiently showing to promote the effect of cross-linking reaction, Relative to every 100 mass parts of rubber total amount, the mixed ratio of thiazole system promotor be preferably 0.5 mass parts or more, 2 mass parts with Under.In addition, relative to every 100 mass parts of rubber total amount, the mixed ratio of thiuram system promotor is preferably 0.5 mass parts or more 2 below the mass.
< foaming ingredient >
As foaming ingredient, the foaming agent that gas is generated by heat resolve is used.
(foaming agent)
As foaming agent, the various compounds that gas is generated by heat resolve can be used.It, can be with as foaming agent Enumerate such as 4,4 '-oxos bis- (benzene sulfonyl hydrazides) (OBSH), azodicarbonamide (ADCA), N, N- dinitroso pentamethylene four It is one kind or two or more in amine (DPT) etc..Particularly preferred OBSH.
Relative to every 100 mass parts of rubber total amount, the mixed ratio of the foaming agents such as OBSH is preferably 1 mass parts or more, excellent It is selected as 4 below the mass.When the mixed ratio of foaming agent is less than the range, between the blowing-agent particle in conductive rubber composition Distance increase, cannot sufficiently obtain be with each blowing-agent particle originate from adjacent foam bubble due to mutual exapnsion power and Mutually inhibit the effect of expansion.Therefore, the bubble diameter of foam bubble as a whole increases, the flatness drop of the outer peripheral surface of roller main body It is low, it is possible to the effect to form the image quality of image cannot be improved.
In addition, since conductive rubber composition can not be made sufficiently to foam, thus the roller main body after crosslinking and foaming becomes It is really up to the mark, it is also possible to the flexibility of the appropriateness of transfer roll cannot be suitable as.In addition, being described above when foaming insufficient Reduction using material and cut down the manufacturing cost of transfer roll effect and carry out transfer roll lightweight and cut down traffic expense With etc. costs effect be also possible to it is insufficient.
On the other hand, it is above-mentioned to continue swollen due to foaming in the case that the mixed ratio of foaming agent is more than above range Swollen adjacent foam bubble mutually inhibits the effect of expansion too strong due to mutual exapnsion power, and each bubble diameter becomes too small, hands over Roller main body after connection and foaming can be hardened instead, it is possible to cannot be suitable for the flexibility of the appropriateness of transfer roll.
In contrast, the range by keeping the mixed ratio of foaming agent above-mentioned, it can be ensured that roller main body it is good soft It is soft and make its foam brought by various advantages, while can moderately reduce its foam bubble diameter.
As foaming ingredient, above-mentioned foaming agent can only be used alone, foaming can also be shared together with the foaming agent and helped Agent.
(blowing promotor)
As blowing promotor, the decomposition temperature for reducing combined foaming agent can be used and play and promote the foaming agent The various compounds of the effect of decomposition.As blowing promotor, such as in the case where foaming agent is OBSH, ADCA, preferred urea (H2NCONH2) it is blowing promotor.
Relative to every 100 mass parts of rubber total amount, the mixed ratio of blowing promotor is preferably 2.5 below the mass.It needs Illustrate, the lower limit of the mixed ratio of blowing promotor is 0 mass parts.
Other > of <
In conductive rubber composition, it can according to need further mixed various additives.It, can be with as additive It enumerates such as crosslinking accelerating auxiliaries, antacid, filler, plasticizer, processing aid, resist degradation agent.
Wherein, as crosslinking accelerating auxiliaries, it can be cited for example that the metallic compounds such as zinc oxide (zinc white)；Stearic acid, oil The fatty acid such as acid, cottonseed fatty acid；And it is one kind or two or more in conventionally known crosslinking accelerating auxiliaries.It is total relative to rubber Measure every 100 mass parts, the mixed ratio for being crosslinked accelerating auxiliaries is respectively preferably 0.1 mass parts or more, preferably 7 mass parts with Under.
The effect of antacid is to prevent to be produced from epichlorohydrin rubber, the chlorine system gas residue of CR in roller in crosslinking In main body and thus crosslinking, pollution photoreceptor etc. are hindered caused by.As antacid, it can be used to play as acid acceptor and make Various substances, wherein it is preferred that dispersed excellent hydrotalcite or MAGSARAT, particularly preferred hydrotalcite.
In addition, if hydrotalcite etc. and magnesia, potassium oxide are shared, can obtain it is higher by sour effect, can Further it is reliably prevented the pollution of photoreceptor.Relative to every 100 mass parts of rubber total amount, the mixed ratio of antacid is preferred More than 0.1 mass parts, preferably 7 below the mass.
As filler, it can be cited for example that zinc oxide, silica, carbon black, clay, talcum, calcium carbonate, magnesium carbonate, hydrogen It is one kind or two or more in aluminium oxide etc..By mixed filler, the mechanical strength etc. of transfer roll can be improved.
In addition, roller main body electron conduction can be assigned if using conductive carbon black as filler.As electric conductivity Carbon black, such as preferred HAF.HAF can be dispersed in conductive rubber composition, it is thus possible to assign transfer roll as far as possible Uniform electron conduction.Relative to every 100 mass parts of rubber total amount, the mixed ratio of conductive carbon black is preferably 1 mass parts More than, preferably 10 below the mass.
As plasticizer, it can be cited for example that dibutyl phthalate, dioctyl phthalate, tripotassium phosphate phenol Various waxes such as the various plasticizer such as ester, polar waxes etc..In addition, as processing aid, it can be cited for example that the fat such as zinc stearate Acid metal salt etc..Relative to every 100 mass parts of rubber total amount, the mixed ratio of plasticizer and/or processing aid is preferably 3 mass Part or less.
As resist degradation agent, various age resisters, antioxidant etc. can be enumerated.Wherein, age resister reduces transfer roll Roller resistance value environmental factor dependence, while also acting as the effect of the rising for the roller resistance value for inhibiting continuous when being powered.As anti- Aging agent, it can be cited for example that nickel diethyl dithiocarbamate, nickel dibutyl dithiocarbamate etc..Relative to rubber Every 100 mass parts of total amount, the mixed ratio of age resister are preferably 0.1 mass parts or more, and preferably 1 below the mass.
It, can be further with arbitrary ratio mixture antiscorching agent, lubricant, pigment, antistatic in addition, as additive The various additives such as agent, fire retardant, neutralizer, nucleating agent, co-crosslinker.
" transfer roll "
Fig. 1 is the perspective view for showing an example of embodiment of transfer roll of the invention.
Referring to Fig.1, the transfer roll 1 of this example has roller main body 2, and the roller main body 2 is by the electric conductivity rubber comprising above-mentioned each ingredient The crosslinking of glue composition, foamed (for cross-linking agent and being foamed) are formed as the tubular of Porous and single layer.In roller main body 2 Insert is fixed with axis 4 in the through-hole 3 at center.
Axis 4 is integrally formed such as the metal as aluminium, aluminium alloy, stainless steel.
Axis 4 is for example electrically engaged by conductive bonding agent and roller main body 2, while mechanically being fixed, or The axis of internal diameter of the person by the way that outer diameter to be greater than to through-hole 3 electrically engages and being pressed into through-hole 3 with roller main body 2, while by with machinery side Formula is fixed.Or both modes can also be shared and electrically engage axis 4 and roller main body 2, it is mechanically fixed.
It the use of extruder is first cylinder by the conductive rubber composition extrusion molding of preparation in the manufacture of transfer roll 1 Next shape is cut into defined length, pressurize, heat in vulcanizing tank, make rubber cross and foam.
Next, carrying out heating to the cylindrical body after crosslinking, foaming using baking oven etc. makes its secondary cross-linking, to roller after cooling The outer peripheral surface 5 of main body 2 is ground, and defined outer diameter is become.
It, can be using the various grinding method such as the crosscutting grinding of dry type as grinding method.
Axis 4 can be fixed in through-hole 3 after the cutting from cylindrical body to any time insert after grinding.
But after dicing, secondary cross-linking and grinding are preferably carried out with state axis 4 being inserted into through-hole 3 first.By This, the warpage of roller main body 2 caused by dilation when being able to suppress secondary cross-linking, deformation.In addition, being with axis 4 by one side Center is rotated is ground on one side, be can be improved the workability of the grinding and is able to suppress the runout of outer peripheral surface 5.
About axis 4, as noted, can by outer diameter be greater than through-hole 3 internal diameter axis be pressed into through-hole 3 or In the through-hole 3 of cylindrical body before being inserted into secondary cross-linking by conductive Thermocurable bonding agent.
In the former case, it completes be pressed into axis 4 while electrically engaging and being mechanically fixed with roller main body 2.
In addition, in the latter case, by the heating in baking oven, secondary cross-linking, while Thermocurable occur for cylindrical body Bonding agent is cured, which electrically engages with roller main body 2, while mechanically being fixed.
Alternatively, it is also possible to as described above share both modes, electrically engages axis 4 with roller main body, be mechanically fixed.
It should be noted that in the embodiment of figure 1, roller main body 2 is by the specific rubber group comprising above-mentioned each ingredient Close the crosslinking of object, the single layer structure that foamed is constituted, but roller main body may be 2 layers or more of laminated structure.In this case, As long as forming the outermost layer for constituting outer peripheral surface i.e. by the crosslinking of the specified rubber composition comprising above-mentioned each ingredient, foamed It can.
" roller resistance value "
The variation > of < roller resistance value due to caused by the difference of use environment
Fig. 2 is the figure being illustrated to the method for the roller resistance value of measurement transfer roll.
Referring to Fig.1, Fig. 2 is evaluated based on the roller resistance value measured using following methods due to using ring in the present invention The variation of the roller resistance value of transfer roll 1 caused by the difference in border.
That is, preparing the aluminium drum 6 that can be rotated with certain rotation speed, make the roller main body 2 for measuring the transfer roll 1 of roller resistance value Outer peripheral surface 5 abutted from top with the outer peripheral surface 7 of the aluminium drum 6.
In addition, DC power supply 8 and resistance 9 are connected in series between the axis 4 and aluminium drum 6 of transfer roll 1, measuring circuit is constituted 10.(-) side of DC power supply 8 is connect with axis 4, and (+) side is connect with resistance 9.The resistance value r of resistance 9 is according to the water of roller resistance value It puts down and is adjusted in the range of 100 Ω~10k Ω, so that the effective digital of the measured value of the roller resistance value increases as far as possible.
Next, the both ends of axis 4 are applied with the load F of 500g respectively, in the state for making roller main body 2 be crimped to aluminium drum 6 Under, so that aluminium drum 6 is rotated (revolving speed: 30rpm), while from DC power supply 8 to the application voltage E for applying direct current 2000V between the two, 30 Measurement is applied to the detection voltage V of resistance 9 after second.
According to the detection voltage V of measurement and apply voltage E (=2000V), the roller resistance value R of transfer roll 1 substantially can be by Formula (i ') is found out.
R=r × E/V-r (i ')
Wherein, due to-the r in formula (i ') this can be considered as it is small, thus in the present invention can also be by formula (i) roller resistance value of the value found out as transfer roll 1.
Formula (i): R=r × E/V (i)
10 DEG C of temperature, relative humidity 20% low temperature and low humidity environment under and 30 DEG C of temperature, relative humidity 80% high temperature Under high humidity environment, implement the measurement of roller resistance value R, finds out the roller resistance value R under low temperature and low humidity environmentLL(Ω) and high temperature and humidity Roller resistance value R under environmentHH(Ω)。
Also, find out the logarithm logR of two roller resistance valuesLLAnd logRHHDifference logRLL-logRHH, which is less than 1.4 the case where, is evaluated as changing small (zero), is evaluated as changing big (×) for 1.4 or more situation.
It will also realize that by the result of aftermentioned embodiment, in transfer roll 1 of the invention, above-mentioned difference is 1.8 hereinafter, can comment Valence is that the variation of the roller resistance value due to caused by the difference of use environment is small.
The rising > of roller resistance value when < is continuously powered
Referring again to Fig. 1, Fig. 2, to the both ends of axis 4 point under 23 DEG C of temperature, the room temperature of relative humidity 55%, normal wet environment Not Shi Jia 500g load F, in the state of making roller main body 2 be crimped to aluminium drum 6, from DC power supply 8 to continuously applying between the two Add the application voltage E of direct current 2000V.During the continuous energization, aluminium drum 6 stops rotating, and the same area of roller main body 2 is maintained to begin The state contacted eventually with aluminium drum 6.The resistance value r of resistance 9 according to roller resistance value level in the range of 100 Ω~10k Ω into Row adjustment, so that the effective digital of the measured value of the roller resistance value increases as far as possible.
Next, record is applied to the passage of the detection voltage V of resistance 9 after being just initially powered up, finds out energization and start When roller resistance value R0(Ω) and from be powered by 30 minutes at the time of roller resistance value R30(Ω)。
Also, find out the ratio between two roller resistance values R30/R0As the increase ratio of roller resistance value, by the increase ratio less than 1.5 Situation is evaluated as rising small (zero), is evaluated as rising big (×) for 1.5 or more situation.
It will also realize that by the result of aftermentioned embodiment, in transfer roll 1 of the invention, which is 2 hereinafter, can be evaluated as The rising of roller resistance value when continuous energization is small.
" image forming apparatus "
Image forming apparatus of the invention is characterized in that, is assembled with transfer roll of the invention.As figure of the invention As forming device, it can be cited for example that laser printer, electrostatic duplicator, plain paper facsimile device or their compounding machine Deng the various image forming apparatuses for utilizing xerography.
Embodiment
The present invention is further illustrated below based on embodiment, comparative example, but composition of the invention is not necessarily limited to these.
1 > of < embodiment
As rubber, GECO [HYDRIN (registered trademark) T3108 of Japanese Zeon Co., Ltd. manufacture] 20 mass are shared Part and NBR [JSR N250SL, non-oil-filled, the low nitrile NBR, acrylonitrile content: 20%] 80 mass parts of JSR Corp.'s manufacture.
Also, two kinds of 100 mass parts of rubber total amount are plasticated using banbury mixers, at the same the following each ingredients of mixture into Row is kneaded.
[table 1]
Ingredient Mass parts
Filler 10
Foaming agent 4
Sylvite 1
Crosslinking accelerator I 1
Crosslinking accelerator II 5
Antacid 1.5
Each ingredient in table 1 is as described below.In addition, the mass parts in table are relative to every 100 mass parts of rubber total amount Mass parts.
Filler: carbon black HAF [SHEAST 3 of Tokai Carbon Co., Ltd.'s manufacture]
Foaming agent: OBSH [Neocellborn (registered trademark) N#1000S of chemical conversion industry Co., Ltd. of Yonghe County manufacture]
Sylvite: bis- (trifluoromethane sulfonyl group) imines potassium [EF-N112 that Mitsubishi Materials electronization is manufactured at Co., Ltd.]
It is crosslinked accelerating auxiliaries I: stearic acid [Tsubaki (つ ば I) of Japan Oil Co's manufacture]
It is crosslinked accelerating auxiliaries II:2 kind zinc oxide [Mitsu Mining & Smelting Co., Ltd's manufacture]
Antacid: hydrotalcite [DHT-4A (registered trademark) -2 of Kyowa Chemical Industry Co., Ltd's manufacture]
It next proceeds to be kneaded, the following crosslinking components of mixture are further kneaded, and prepare conductive rubber composition.
[table 2]
Ingredient Mass parts
Sulphur system crosslinking agent 1.6
Crosslinking accelerator DM 1.6
Crosslinking accelerator TS 2.0
Each ingredient in table 2 is as described below.In addition, the mass parts in table are relative to every 100 mass parts of rubber total amount Mass parts.
Sulphur system crosslinking agent: powder sulphur [manufacture of He Jian chemical industry Co., Ltd.]
DM: two -2-[4-morpholinodithio of crosslinking accelerator based bisulfide [SUNSINE of Shandong Dan County chemical company manufacture MBTS, thiazole system promotor]
Crosslinking accelerator TS: the tetra methylthiuram list sulfide [Sanceler of three new chemical industry Co., Ltd. manufactures (registered trademark) TS, thiuram system promotor]
(transfer roll)
Prepared conductive rubber composition is supplied in extrusion shaping machine, extrusion molding is outer diameterIt is interior DiameterTubular after, be cut into defined length, be mounted on outer diameterCrosslinking on interim axis.
Later, 135 DEG C × 10 minutes pressurized, heateds are carried out using pressurized steam in vulcanizing tank, followed by 160 DEG C × 20 minutes pressurized, heateds, so that cylindrical body is foamed by the gas that the decomposition of foaming agent generates, while making rubber cross.
Next, the cylindrical body is reinstalled in the outer diameter that outer peripheral surface is coated with conductive Thermocurable bonding agentAxis on, in an oven carry out 160 DEG C × 60 minutes heat, make its secondary cross-linking, while making Thermocurable bonding agent Solidification, electrically engages, and mechanically fix with axis.
Then, by after the both ends finishing of cylindrical body, crosscutting grinding is carried out to its outer peripheral surface using cylinder grinder, thus by outer Diameter is finish-machined to(tolerance+0.1mm) forms roller main body, manufactures transfer roll.
2 > of < embodiment
Make 2.5 mass parts of mixed ratio of the foaming agent relative to every 100 mass parts of rubber total amount, in addition to this, with Embodiment 1 is prepared as conductive rubber composition, manufactures transfer roll.
3 > of < embodiment
30 mass parts of amount, the amount of NBR for making GECO are 70 mass parts, while being made relative to every 100 mass of rubber total amount Part sylvite mixed ratio be 0.5 mass parts, foaming agent mixed ratio be 2.5 mass parts, in addition to this, with embodiment 1 It is prepared as conductive rubber composition, manufactures transfer roll.
1 > of < comparative example
30 mass parts of amount, the amount of NBR for making GECO are 70 mass parts, and not mixed sylvite, in addition to this, with implementation Example 1 is prepared as conductive rubber composition, manufactures transfer roll.
2 > of < comparative example
Make 100 mass parts of amount of NBR, not mixed GECO, and makes the sylvite relative to every 100 mass parts of rubber total amount Mixed ratio be that 3 mass parts prepare conductive rubber composition in addition to this similarly to Example 1, manufacture transfer roll.
3 > of < comparative example
Make 1.5 mass parts of mixed ratio of the sylvite relative to every 100 mass parts of rubber total amount, the mix ratio of foaming agent Example is 2.5 mass parts, in addition to this, prepares conductive rubber composition similarly to Example 1, manufactures transfer roll.
4 > of < comparative example
30 mass parts of amount, the amount of NBR for making GECO are 70 mass parts, while being made relative to every 100 mass of rubber total amount The mixed ratio of the foaming agent of part is 0.8 mass parts, and not mixed sylvite is prepared similarly to Example 1 and led in addition to this Electrical rubber composition manufactures transfer roll.
The variation > of < roller resistance value due to caused by the difference of use environment
Using method described above evaluate each embodiment, the transfer roll manufactured in comparative example due to use environment difference The variation (environmental turbulence) of roller resistance value caused by different.
The rising > of roller resistance value when < is continuously powered
Using method described above evaluate each embodiment, the transfer roll manufactured in comparative example continuous energization when roller electricity The rising (be powered and rise) of resistance value.
Above result is listed in table 3.
[table 3]
By the Examples 1 to 3 of table 3, the result of comparative example 1~4 it is found that sharing body in epichlorohydrin rubber and NBR In system, more than 20 mass parts in 100 mass parts of mixed ratio rubber total amount by making epichlorohydrin rubber 30 mass Part is hereinafter, and share potassium relative to every 100 mass parts of rubber total amount 1 range below the mass more than 0.01 mass parts Salt is capable of forming following transfer rolls, and the variation of transfer roll roller resistance value due to caused by the difference of use environment is small, continuous logical The rising of roller resistance value when electric is small, and roller resistance value is stablized, it is thus possible to be formed continuously the image of good quanlity.
4 > of < embodiment
The SBR [SBR1502, non-oil-filled of Sumitomo Chemical Co's manufacture] of mixed equivalent replaces NBR, except this with Outside, conductive rubber composition is prepared similarly to Example 1, manufactures transfer roll.
5 > of < embodiment
Make 2.5 mass parts of mixed ratio of the foaming agent relative to every 100 mass parts of rubber total amount, in addition to this, with Embodiment 4 is prepared as conductive rubber composition, manufactures transfer roll.
6 > of < embodiment
30 mass parts of amount, the amount of SBR for making GECO are 70 mass parts, while being made relative to every 100 mass of rubber total amount Part sylvite mixed ratio be 0.5 mass parts, foaming agent mixed ratio be 2.5 mass parts, in addition to this, with embodiment 4 It is prepared as conductive rubber composition, manufactures transfer roll.
5 > of < comparative example
30 mass parts of amount, the amount of SBR for making GECO are 70 mass parts, and not mixed sylvite, in addition to this, with implementation Example 4 is prepared as conductive rubber composition, manufactures transfer roll.
6 > of < comparative example
Make 100 mass parts of amount of SBR, not mixed GECO, and makes the sylvite relative to every 100 mass parts of rubber total amount Mixed ratio be that 3 mass parts prepare conductive rubber composition in addition to this similarly to Example 4, manufacture transfer roll.
7 > of < comparative example
Make 1.5 mass parts of mixed ratio of the sylvite relative to every 100 mass parts of rubber total amount, the mix ratio of foaming agent Example is 2.5 mass parts, in addition to this, prepares conductive rubber composition similarly to Example 4, manufactures transfer roll.
8 > of < comparative example
30 mass parts of amount, the amount of SBR for making GECO are 70 mass parts, while being made relative to every 100 mass of rubber total amount The mixed ratio of the foaming agent of part is 0.8 mass parts, and not mixed sylvite is prepared similarly to Example 4 and led in addition to this Electrical rubber composition manufactures transfer roll.
For the transfer roll 1 manufactured in the various embodiments described above, comparative example, evaluates the above-mentioned difference due to use environment and draw The rising (be powered and rise) of roller resistance value when the variation (environmental turbulence) of the roller resistance value risen and continuous energization.Result is listed in Table 4.
[table 4]
By the embodiment 4~6 of table 4, the result of comparative example 5~8 it is found that sharing body in epichlorohydrin rubber and SBR In system, also obtain sharing the same result of system with the epichlorohydrin rubber of front and NBR.I.e. it is found that by making ring The mixed ratio of oxygen chloropropane rubber be it is more than 20 mass parts in 100 mass parts of rubber total amount 30 below the mass, and phase 100 mass parts, 1 range below the mass more than 0.01 mass parts every for rubber total amount shares sylvite, is capable of forming following Transfer roll, the variation of transfer roll roller resistance value due to caused by the difference of use environment is small, continuous energization when roller resistance value Rising it is small, roller resistance value stablize, it is thus possible to be continuously formed the image of good quanlity.
In addition, being compared to Examples 1 to 6, as a result further acknowledge, by the way that epichlorohydrin rubber is excellent with cost The high SBR of gesture shares, and shares system compared to NBR, can further reduce cost.
Symbol description
F load
V detects voltage
1 transfer roll
2 roller main bodies
3 through-holes
4 axis
5 outer peripheral surfaces
6 aluminium drum
7 outer peripheral surfaces
8 DC power supplies
9 resistance
10 measuring circuits

Claims (5)

  1. It is crosslinking component it includes rubber, for making the rubber cross, described for making 1. a kind of conductive rubber composition The foaming ingredient of rubber pange and the sylvite in the molecule with fluorine-based and sulfonyl anion, the rubber include to be selected from At least one of group being made of SBR styrene butadiene rubbers and nitrile rubber and epichlorohydrin rubber, the epoxy chlorine The mixed ratio of propane rubber be it is more than 20 mass parts in 100 mass parts of rubber total amount 30 below the mass, and phase 100 mass parts every for the rubber total amount, the mixed ratio of the sylvite be 0.01 mass parts or more 1 below the mass.
  2. 2. conductive rubber composition as described in claim 1, wherein the foaming ingredient includes bis- (the benzene sulphurs of 4,4 '-oxos Hydrazides), relative to every 100 mass parts of the rubber total amount, the mixed ratio of 4, the 4 '-oxo bis- (benzene sulfonyl hydrazides) is 1 mass Part or more 4 below the mass.
  3. 3. conductive rubber composition as claimed in claim 1 or 2, wherein the rubber is further included selected from by ternary At least one of EP rubbers, neoprene and group of acrylic rubber composition.
  4. 4. a kind of transfer roll has the friendship of the conductive rubber composition as described in any one of the claims 1 to 3 The roller main body for the tubular that connection, foamed are constituted.
  5. 5. a kind of image forming apparatus is assembled with transfer roll described in the claims 4.
CN201810268757.7A 2017-05-22 2018-03-29 Conductive rubber composition, transfer roll and image forming apparatus Pending CN108948456A (en)

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